P-Toluenesulfonylhydrazide → HCID 86722489, compound

HRID 718875Notes

Reaction equation

HRID 718875 reaction equation
CC1C=CC(S([NH:11][NH2:12])(=O)=O)=CC=1.[F:13][C:14]1[CH:19]=[CH:18][C:17]([C:20]([C:22]2[N:27]=[CH:26][C:25]3[C@:28]4([CH2:41][C:42]5[CH:47]=[CH:46][CH:45]=[CH:44][N:43]=5)[CH2:40][CH2:39][C:34]5([O:38][CH2:37][CH2:36][O:35]5)[CH2:33][C@H:29]4[CH2:30][CH2:31][CH2:32][C:24]=3[CH:23]=2)=O)=[CH:16][CH:15]=1>CO>[F:13][C:14]1[CH:15]=[CH:16][C:17]([C:20]2[N:11]=[N:12][N:27]3[CH:26]=[C:25]4[C@:28]5([CH2:41][C:42]6[CH:47]=[CH:46][CH:45]=[CH:44][N:43]=6)[CH2:40][CH2:39][C:34]6([O:35][CH2:36][CH2:37][O:38]6)[CH2:33][C@H:29]5[CH2:30][CH2:31][CH2:32][C:24]4=[CH:23][C:22]=23)=[CH:18][CH:19]=1

Participants

4

Reactant 2

HCID 15303P-ToluenesulfonylhydrazideHCID 86722488HCID 86722488, compound

Product 1

HCID 86722489HCID 86722489, compoundYield 100.1%

Reagents, catalysts & solvents 1

HCID 887MethanolSolvent

Conditions

Temperature
50 °C

Procedure

4-Methylbenzenesulfonohydrazide (0.177 g, 0.948 mmol) in MeOH (4 mL) was combined with (4-fluorophenyl)((7aR,11aS)-11a-(pyridin-2-ylmethyl)-5,6,7,7a,8,10,11,11a-octahydrospiro[benzo[6,7]cyclohepta[1,2-c]pyridine-9,2′-[1,3]dioxolan]-3-yl)methanone (0.224 g, 0.474 mmol) and the mixture was stirred at about 50° C. for about 48 h. The reaction mixture was cooled to rt and was washed with sat. aq. NaHCO3 and extracted with DCM (10 mL). The organics were dried over MgSO4 and concentrated in vacuo. The residue was purified on silica gel (12 g) using a gradient of 10-100% EtOAc in heptane to afford (4aR,13bS)-9-(4-fluorophenyl)-13b-(pyridin-2-ylmethyl)-1,2,4,4a,5,6,7,13b-octahydrospiro[benzo[3,4]cyclohepta[1,2-d][1,2,3]triazolo[1,5-a]pyridine-3,2′-[1,3]dioxolane] (156, R1=4-Fluorophenyl, R2=Pyridin-2-ylmethyl) (0.230 g, 56%); LC/MS, method 3, Rt=2.52 min, MS m/z 485 (M+H)+. 1H NMR (400 MHz, DMSO) δ 8.36 (s, 1H), 8.28-8.23 (m, 1H), 8.10-8.02 (m, 3H), 7.80-7.72 (m, 1H), 7.41-7.30 (m, 2H), 7.02-6.97 (m, 1H), 6.57-6.53 (m, 1H), 3.96-3.80 (m, 4H), 3.63-3.54 (m, 1H), 3.52-3.40 (m, 1H), 3.25-3.17 (m, 2H), 2.39-2.34 (m, 1H), 2.21-2.05 (m, 2H), 1.95-1.55 (m, 7H), 1.50-1.37 (m, 1H)

Workup

  1. temperatureThe reaction mixture was cooled to rt
  2. washwas washed with sat. aq. NaHCO3
  3. extractionextracted with DCM (10 mL)
  4. dry with materialThe organics were dried over MgSO4
  5. concentrationconcentrated in vacuo
  6. customThe residue was purified on silica gel (12 g)

Sources & evidence

ORD record
ord-f76ec4528ef24fa6940cde1cf1c4bc3f
Source dataset
uspto-grants-2015_11
Patent number
US09193744B2

Reaction notes

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